JP4755919B2 - Lead zirconate titanate composition, method for producing the same, piezoelectric body, and piezoelectric element - Google Patents

Description

The present invention relates to a lead zirconate titanate composition comprising PNN-PZT (Pb (Ni, Nb) O ₃ —PbZrO ₃ —PbTiO ₃ ) as a main component, a method for producing the same, a piezoelectric body comprising the composition, and this The present invention relates to a piezoelectric element using a piezoelectric body.

  A piezoelectric element having a piezoelectric material having a piezoelectric property that expands and contracts as the electric field application intensity increases and decreases and an electrode that applies an electric field to the piezoelectric material is used for applications such as an ink jet recording head and an ultrasonic probe. in use.

  As the piezoelectric material, composite oxides having a perovskite structure such as lead zirconate titanate (PZT) are widely used. PZT-based piezoelectric bodies are usually manufactured by firing at a high temperature of 1200 to 1400 ° C.

  In view of energy efficiency and the like, it is preferable that firing can be performed at a lower temperature. In addition, the piezoelectric body may be directly formed on the substrate on which the electrode or the like is formed by a liquid phase method such as a sol-gel method or an organometallic decomposition method. In such a case, the influence on the substrate is reduced. Therefore, it is preferable that firing can be performed at a lower temperature.

In Patent Document 1, the firing temperature is set by adding AgO to Pb (Zn, Nb) O ₃ —Pb (Sn, Nb) O ₃ —PbZrO ₃ —PbTiO ₃ [PZN—PSnN—PZT]. It is disclosed that it can be reduced and baking at 970 to 1070 ° C. becomes possible.

In Patent Document 2, Pb (Ni, Nb) O ₃ —PbZrO ₃ —PbTiO ₃ [PNN-PZT] is compared to Pb (B1 _1/2 B2 _1/2 ) O ₃ [wherein B1 = Ni and It is disclosed that by adding [// Zn, B2 = W and / or Mo], the firing temperature can be lowered and firing at 950 ° C. becomes possible.
JP-A-10-316467 JP 2002-226266 A

  In Patent Documents 1 and 2, firing at 1000 ° C. or lower is realized, but a firing temperature exceeding 900 ° C. is still necessary. Piezoelectric materials having a piezoelectric constant that is practically necessary for firing at a low temperature of 900 ° C. or lower are not limited to PZT systems and have not been reported in the past.

The present invention has been made in view of the above circumstances, and a lead zirconate titanate composition that can be fired at a low temperature of 900 ° C. or less and has practically necessary piezoelectricity when used as a piezoelectric body, and its production. It is intended to provide a method.
Another object of the present invention is to provide a piezoelectric body that can be fired at a low temperature of 900 ° C. or lower and has a piezoelectricity that is practically necessary, and a piezoelectric element using the piezoelectric body.

The lead zirconate titanate composition of the present invention is
For ternary lead zirconate titanate (X) represented by the general formula Pb (Ni, Nb) O ₃ —PbZrO ₃ —PbTiO ₃ ,
(A) component: Pb in excess of the stoichiometric ratio;
(B) component: Zn,
Component (C) is characterized in that at least one rare earth element selected from the group consisting of Ce, Yb, and Dy is added.

  The lead zirconate titanate-based composition of the present invention can take any form such as a bulk body such as a sintered body, a pulverized product thereof, a film, or the like.

The method for producing the lead zirconate titanate composition of the present invention is the method for producing the lead zirconate titanate composition of the present invention,
A molding step of compression-molding a raw material powder containing the constituent elements of ternary lead zircon titanate (X) and the components (A) to (C) into a predetermined shape;
And a firing step of firing the compression-molded body obtained in the molding step.

The piezoelectric body of the present invention is
For ternary lead zirconate titanate (X) represented by the general formula Pb (Ni, Nb) O ₃ —PbZrO ₃ —PbTiO ₃ ,
(A) component: Pb in excess of the stoichiometric ratio;
(B) component: Zn,
Component (C) is characterized in that at least one rare earth element selected from the group consisting of Ce, Yb, and Dy is added.

In the present invention, a piezoelectric body having a firing temperature of 800 to 900 ° C. during manufacture and a piezoelectric constant d ₃₃ of 600 pm / V or more can be realized.

Regardless of the composition, the piezoelectric body itself having the piezoelectric constant at the firing temperature is novel.
In other words, a piezoelectric body characterized in that the firing temperature during production is 800 to 900 ° C. and the piezoelectric constant d ₃₃ is 600 pm / V or more is novel and is included in the present invention.

“Piezoelectric constant d ₃₃ ” is a displacement amount (pm / V) per unit applied voltage of the piezoelectric body when a predetermined voltage is applied to the piezoelectric body. In this specification, a displacement amount (pm / V) of a piezoelectric body when a predetermined voltage is applied to the piezoelectric body is measured using a “laser displacement meter FCE-1” manufactured by Toyo Technica Co., Ltd. Let d ₃₃ be determined.

  A piezoelectric element according to the present invention includes the piezoelectric body according to the present invention and an electrode that applies an electric field to the piezoelectric body.

According to the present invention, it is possible to realize a lead zirconate titanate-based composition that can be fired at a low temperature of 900 ° C. or lower and has piezoelectricity that is practically necessary when used as a piezoelectric body.
According to the present invention, a piezoelectric body that can be fired at a low temperature of 900 ° C. or lower and has a piezoelectricity that is practically necessary can be realized. In the present invention, a piezoelectric body having a firing temperature of 800 to 900 ° C. during manufacture and a piezoelectric constant d ₃₃ of 600 pm / V or more can be realized.

The lead zirconate titanate composition of the present invention is a PNN-PZT composition,
For ternary lead zirconate titanate (X) represented by the general formula Pb (Ni, Nb) O ₃ —PbZrO ₃ —PbTiO ₃ ,
(A) component: Pb in excess of the stoichiometric ratio;
(B) component: Zn,
Component (C) is characterized in that at least one rare earth element selected from the group consisting of Ce, Yb, and Dy is added.

In the ternary lead zirconate titanate (X), the molar ratio of the Pb (Ni, Nb) O ₃ component, the PbZrO ₃ component, and the PbTiO ₃ component is appropriately designed and is not particularly limited.
In the ternary lead zirconate titanate (X), the molar ratio of Ni and Nb in the Pb (Ni, Nb) O ₃ component is appropriately designed and is not particularly limited. The number of moles of Ni in Pb (Ni, Nb) O ₃ is preferably 1/3 and the number of moles of Nb is preferably 2/3.

  The present inventor improves the sinterability by adding the above components (A) to (C) to the ternary lead zirconate titanate (X) and realizes low-temperature firing at 900 ° C. or lower. I find out what I can do. Specifically, it has been found that a lead zirconate titanate-based composition having piezoelectricity that is practically necessary when used as a piezoelectric body can be realized by low-temperature firing at 700 to 900 ° C. Even if any of the above components (A) to (C) is missing, such an effect cannot be obtained.

  The timing of adding the components (A) to (C) is not limited, and may be the same as the preparation of the three-component lead zirconate titanate (X) or after the preparation of the three-component lead zirconate titanate (X).

  The lead zirconate titanate-based composition of the present invention can take any form such as a bulk body such as a sintered body, a pulverized product thereof, a film, or the like.

  As a form of the lead zirconate titanate composition of the present invention, for example, a raw material powder containing a component element of ternary lead zirconate titanate (X) and the components (A) to (C) is compression molded into a predetermined shape. And the sintered compact manufactured by baking the obtained compression molding body is mentioned.

  The raw material powder can contain the components (A) to (C) in the form of oxides and / or acid salts (for example, nitrates and sulfates).

  The raw material powder is preferably a mixed powder of a powder of ternary lead zirconate titanate (X), a powder containing the component (A), a powder containing the component (B), and a powder containing the component (C). . In this case, the three-component lead zirconate titanate (X) powder may be prepared in advance, or may be prepared from the raw material powder of the three-component lead zirconate titanate (X). . The powder may be mixed by dry mixing or wet mixing.

  In the lead zirconate titanate-based composition of the present invention, the addition amount of the component (A) is more than 0 parts by mass and less than 8.0 parts by mass in terms of oxide amount with respect to 100 parts by mass of the component (X). Component B) is added in an amount of 0 to 4.0 parts by mass in terms of oxide, and component (C) is added in an amount of 0 to 2.0 parts by mass in terms of oxide. It is preferable.

  In the lead zirconate titanate-based composition of the present invention, the amount of component (A) added is 1.0 part by mass or more and 3.0 parts by mass or less in terms of oxide amount with respect to 100 parts by mass of component (X). The amount of component (B) added is 0.5 parts by mass or more and 1.5 parts by mass or less in terms of oxide amount, and the amount of component (C) added is 0.25 parts by mass or more in terms of oxide amount. More preferably, it is 75 parts by mass or less.

  In the lead zirconate titanate-based composition of the present invention, the addition amount of the component (A) is 2.0 parts by mass in terms of oxide amount with respect to 100 parts by mass of the component (X), and the addition of the component (B) It is particularly preferable that the amount is 1 part by mass in terms of oxide amount, and the amount of component (C) added is 0.5 parts by mass in terms of oxide amount.

The “addition amount in terms of oxide amount” is a conversion in terms of the oxide amount when the above components are added in the form of an oxide. That is, the addition amount of the component (A) is converted by the PbO amount, and the addition amount of the component (B) is converted by the ZnO amount. When the component (C) contains Ce as the component (C), the amount is converted to the amount of CeO _{2. When the} component (C) contains Dy, the amount is the amount of Dy ₂ O ₃ . When the component (C) contains Yb, the amount is converted by the amount of Yb ₂ O ₃ .

  In the lead zirconate titanate-based composition of the present invention, the firing temperature can be as low as 900 ° C. or lower, specifically 700 to 900 ° C., preferably 800 to 900 ° C. In the present invention, the piezoelectricity that is practically necessary when used as a piezoelectric body can be realized even by such low-temperature firing. The firing may be performed in a plurality of stages by dividing into preliminary firing and main firing. In this case, the firing temperature means “main firing temperature”.

  The firing atmosphere is not limited, and an oxygen-containing atmosphere such as air is preferable. The inventor has found that the piezoelectric constant decreases in an inert atmosphere such as Ar (see Example 22).

  The lead zirconate titanate composition of the present invention may contain inevitable impurities in addition to the essential components (X) and (A) to (C). Moreover, the lead zirconate titanate-based composition of the present invention can contain optional components such as various additives within a range that does not significantly impair the effects of the present invention.

  The lead zirconate titanate-based composition of the present invention achieves low-temperature firing at 900 ° C. or less without greatly impairing the piezoelectricity inherent in PNN-PZT. The lead zirconate titanate composition of the present invention is advantageous in terms of energy efficiency and energy cost. In addition, when a piezoelectric body composed of the lead zirconate titanate composition of the present invention is directly formed on a substrate on which an electrode or the like is formed by a liquid phase method such as a sol-gel method or an organometallic decomposition method, The effect of heat on the substrate can be reduced, which is preferable.

"Production Method of Lead Zirconate Titanate Composition"
The method for producing the lead zirconate titanate composition of the present invention is the method for producing the lead zirconate titanate composition of the present invention,
A molding step of compression-molding a raw material powder containing the constituent elements of ternary lead zircon titanate (X) and the components (A) to (C) into a predetermined shape;
And a firing step of firing the compression-molded body obtained in the molding step.

  In the firing step, the compression-molded body can be fired at a low temperature of 700 to 900 ° C, preferably 800 to 900 ° C. In the firing step, the compression molded body is preferably fired in an oxygen-containing atmosphere such as air.

"Piezoelectric body"
The piezoelectric body of the present invention is
For ternary lead zirconate titanate (X) represented by the general formula Pb (Ni, Nb) O ₃ —PbZrO ₃ —PbTiO ₃ ,
(A) component: Pb in excess of the stoichiometric ratio;
(B) component: Zn,
Component (C) is characterized in that at least one rare earth element selected from the group consisting of Ce, Yb, and Dy is added.

In the present invention, the firing temperature can be as low as 900 ° C. or lower, specifically 700 to 900 ° C., preferably 800 to 900 ° C. In the present invention, a piezoelectric body having a firing temperature of 800 to 900 ° C. during manufacture and a piezoelectric constant d ₃₃ of 600 pm / V or more can be realized.

Regardless of the composition, the piezoelectric body itself having the piezoelectric constant at the firing temperature is novel.
In other words, a piezoelectric body characterized in that the firing temperature during production is 800 to 900 ° C. and the piezoelectric constant d ₃₃ is 600 pm / V or more is novel and is included in the present invention.

"Piezoelectric element"
A piezoelectric element according to the present invention includes the piezoelectric body according to the present invention and an electrode that applies an electric field to the piezoelectric body.

  Hereinafter, an embodiment of the piezoelectric element of the present invention will be described with reference to the drawings. An ink jet recording head will be described as an example. FIG. 1 is a sectional view (a sectional view in the thickness direction of a piezoelectric element) of an ink jet recording head provided with the piezoelectric element of the present invention.

  A piezoelectric element 1 shown in FIG. 1 is an element in which a lower electrode 3, a piezoelectric body 4 having the above composition, and an upper electrode 5 are sequentially formed on the surface of a substrate 2 such as a silicon wafer. An electric field is applied to the piezoelectric body 4 in the thickness direction by the lower electrode 3 and the upper electrode 5.

  The form of the piezoelectric body 4 is appropriately designed and may be a bulk body or a film. For example, the piezoelectric element 1 can be manufactured by forming the electrodes 3 and 5 on the piezoelectric body 4 made of a sintered body and then bonding the substrate 2. Also, a bulk body or a film piezoelectric body 4 is directly formed on the substrate 2 on which the lower electrode 3 is formed by a known method such as a sol-gel method or a liquid phase method such as an organometallic decomposition method, and the upper electrode is formed thereon. 5 can be formed to manufacture the piezoelectric element 1.

The material for the electrodes 3 and 5 is not particularly limited, and examples thereof include metals such as Ag, Pt, Ir, IrO ₂ , RuO ₂ , LaNiO ₃ , SrRuO ₃ , and combinations thereof. The material of the electrode 3 and the electrode 5 may be the same or non-identical.

  The piezoelectric element 1 is driven by a control means (not shown) such as a drive circuit that controls increase / decrease in the electric field application intensity between the electrodes 3 and 5.

  In the ink jet recording head, an ink storing and discharging member 9 having an ink chamber 7 for storing ink and an ink discharging port 8 is attached to the back surface of the substrate 2 of the piezoelectric element 1 having the above-described configuration via a vibration plate 6. The diaphragm 6 is not provided separately, and the substrate 2 may also serve as the diaphragm. In the ink jet recording head, the electric field strength applied to the piezoelectric element 1 is increased or decreased to expand and contract the piezoelectric element 1, thereby controlling the ejection of ink from the ink chamber 7 and the ejection amount.

  Since the piezoelectric element 1 includes the piezoelectric body 4 of the present invention, the piezoelectric element 1 has practically necessary piezoelectricity, and can be formed by low-temperature firing, so that in terms of energy efficiency and energy cost, etc. It is advantageous. Further, when the piezoelectric body 4 having the above composition is directly formed on the substrate 2 on which the lower electrode 3 is formed by a liquid phase method such as a sol-gel method or an organometallic decomposition method, it can be fired at a lower temperature than in the past. The influence of heat on the substrate 2 and the like can be reduced, which is preferable.

  Examples and comparative examples according to the present invention will be described.

(Examples 1 to 15)
First, PbO powder, NiO powder, Nb ₂ O ₅ powder, ZrO ₂ powder, and TiO ₂ powder are used as the raw material powder of the component (X) (all have a purity of 99.99% or more). Each was weighed so as to have a composition, and these were thoroughly dry-mixed by a ball mill using ZrO ₂ balls. The obtained mixed powder was calcined at 800 ° C. for 5 hours in an air atmosphere to obtain a powder of ternary lead zirconate titanate (X). 3 Composition of component lead zirconate titanate (X) _was set to _{0.5Pb (Ni, Nb) O 3} -0.15PbZrO 3 -0.35PbTiO 3 (X-1).

PbO powder that is a powder containing the component (A) and ZnO that is a powder containing the component (B) in the amounts shown in Tables 1 and 2 with respect to the powder of the above three-component lead zirconate titanate (X) The same ball mill as described above is added to the powder and any one of CeO ₂ powder, Dy ₂ O ₃ powder, and Yb ₂ O ₃ powder, which is a powder containing component (C), each having a purity of 99.99% or more Was thoroughly dry-mixed. In the table, the addition amount of the components (A) to (C) is an oxide equivalent amount (parts by mass) when the component (X) is 100 parts by mass.

The obtained mixed powder was uniaxially compression molded at a pressure of 50 MPa. The obtained compression-molded body was fired at 800 ° C. in an air atmosphere to obtain a sintered body made of the lead zirconate titanate-based composition of the present invention containing the components (X) and (A) to (C). The surface of the sintered body was polished to obtain a piezoelectric body. The lower and upper electrodes are formed by applying and baking Ag paste on the upper and lower surfaces of the obtained piezoelectric body, and a known single polarization process is performed on these electrodes to thereby obtain the piezoelectric element of the present invention. Got. Obtained by cutting the piezoelectric element was measured piezoelectric constant d _33.

(Examples 16 to 18)
Except that the composition of the ternary lead zirconate titanate (X) was 0.35Pb (Ni, Nb) O ₃ −0.27PbZrO ₃ −0.38PbTiO ₃ (X-2), the same as in Examples 1 to 15 Thus, a sintered body, a piezoelectric body, and a piezoelectric element made of the lead zirconate titanate composition of the present invention were obtained and evaluated in the same manner.

(Example 19)
(A) to (C) components are all added in the form of nitrate, and ternary lead zirconate titanate (X) powder and powder containing (A) to (C) components are wet-mixed and mixed A sintered body comprising the lead zirconate titanate-based composition of the present invention, a piezoelectric body, and the same as in Examples 1 to 15 except that the liquid component was removed later with a rotary evaporator and then compression molding was performed. A piezoelectric element was obtained and evaluated in the same manner.

(Examples 20 and 21)
A sintered body, a piezoelectric body, and a piezoelectric element made of the lead zirconate titanate-based composition of the present invention were obtained in the same manner as in Examples 1 to 15 except that the firing temperature was changed to the temperature shown in Table 2. Similarly, evaluated.

(Example 22)
A sintered body, a piezoelectric body, and a piezoelectric element made of the lead zirconate titanate-based composition of the present invention were obtained in the same manner as in Examples 1 to 15, except that the firing atmosphere of the compression molded body was an Ar atmosphere. Evaluated.

(Comparative Example 1)
For comparison, in the same manner as in Examples 1 to 15, except that none of the components (A) to (C) was added to the ternary lead zirconate titanate (X) and the firing temperature was 1250 ° C. A sintered body, a piezoelectric body, and a piezoelectric element made of the lead zirconate titanate composition were obtained and evaluated in the same manner.

(Comparative Example 2)
A sintered body, a piezoelectric body, and a piezoelectric element made of a comparative lead zirconate titanate-based composition were obtained in the same manner as in Comparative Example 1 except that the firing temperature was set to 800 ° C. as in Examples 1 to 15. Evaluation was performed in the same manner.

(Comparative Examples 3-5)
The lead zirconate titanate for comparison is the same as in Examples 1 to 15 except that any of the components (A) to (C) is not added and the composition of the additive components is as shown in Table 3. A sintered body, a piezoelectric body, and a piezoelectric element made of the composition were obtained and evaluated in the same manner.

(result)
The evaluation results are shown in Tables 1 to 3.

In Comparative Example 1, the components (A) to (C) were not added and fired at a high temperature as in the past (firing temperature 1250 ° C.). In Comparative Example 1, since high temperature firing was performed, a high piezoelectric constant (d ₃₃ = 700 pm / V) was obtained without adding the components (A) to (C). This is the piezoelectricity inherent to PNN-PZT.

However, in Comparative Example 2 (baking temperature 800 ° C.) fired at a low temperature with the same composition as Comparative Example 1, the piezoelectric constant d ₃₃ was 70 pm / V, and the piezoelectric constant was extremely low. In Comparative Examples 3 to 5 (firing temperature 800 ° C.) in which only two components (A) to (C) were added, although the piezoelectric constant was improved from Comparative Example 2, the piezoelectric constant d ₃₃ was 330 pm at the maximum. / V.

In contrast, in Examples 1 to 20 in which the components (A) to (C) were added to the three-component lead zirconate titanate (X), both were fired at a low temperature of 800 to 900 ° C. A piezoelectric constant higher than that of Comparative Example 2 is obtained, d ₃₃ ≧ 500 pm / V is realized, and d ₃₃ ≧ 600 pm / V is also realized. In particular, with respect to 100 parts by mass of component (X), the amount of component (A) added is 2.0 parts by mass, the amount of component (B) added is 1.0 part by mass, and the amount of component (C) added In Example 1 in which 0.5 part by mass was added (addition amount was converted to an oxide amount), the piezoelectric constant d ₃₃ = 680 pm / V, and a piezoelectric constant substantially equivalent to that of Comparative Example 1 subjected to high-temperature firing was obtained.

  Examples 2 to 9 are examples in which the total addition amount of the components (A) to (C) was changed while the mixing ratio of the components (A) to (C) was the same as that in Example 1. In Examples 1-9, when the total addition amount of (A)-(C) component of Example 1 is set to 1, the relationship between the total addition amount T of (A)-(C) component and a piezoelectric constant is shown. It is shown in 2. For example, T = 0.25 is Example 2, T = 0.5 is Example 3, T = 1 is Example 1, T = 2 is Example 7, T = 4 is Example 8, and T = 8 is. This corresponds to Example 9.

  FIG. 2 shows that the piezoelectric constant gradually decreases as the deviation from Example 1 in which the highest piezoelectric constant is obtained.

The present inventor shows that the piezoelectric constant d ₃₃ is expressed by the following formula, and therefore, the relative permittivity decreases as the total amount of the components (A) to (C) increases, and the piezoelectric constant tends to decrease. I think there is.
d ₃₃ = k ₃₃ (ε / s) ^1/2
(Wherein k ₃₃ : electromechanical coupling constant, ε: relative dielectric constant, s: elastic constant)

Specifically, in Examples 1 to 9, when 0 <T ≦ 4, that is, with respect to 100 parts by mass of the (X) component, the addition amount of the component (A) is more than 0 parts by mass to 8.0 parts by mass. The addition amount of the component (B) is more than 0 parts by mass and less than 4.0 parts by mass, and the addition amount of the component (C) is more than 0 parts by mass and less than 2.0 parts by mass (both are oxide amounts) D ₃₃ ≧ 500 pm / V is realized.

In Examples 1 to 9, when 0.5 <T ≦ 1.5, that is, with respect to 100 parts by mass of component (X), the amount of component (A) added is 1.0 part by mass or more and 3.0 parts by mass. The amount of component (B) added is 0.5 parts by mass or more and 1.5 parts by mass or less, and the amount of component (C) added is 0.25 parts by mass or more and 0.75 parts by mass or less. (Both in terms of oxide amount) d ₃₃ ≧ 600 pm / V or more is realized.

  In Examples 10 and 11 in which the type of component (C) was changed, the same results as in Examples 1 to 9 were obtained. In Examples 12 to 15 in which the mixing ratios of the components (A) to (C) were changed, the same results as in Examples 1 to 9 were obtained. In Examples 16 to 18 in which the composition of the component (X) was changed, the same results as in Examples 1 to 9 were obtained.

  Moreover, it became clear from comparison with Examples 1-21 and Example 22 that oxygen-containing atmospheres, such as an air atmosphere, are suitable as baking atmosphere.

  The lead zirconate titanate-based composition of the present invention can be preferably used for an actuator mounted on an ink jet recording head, a magnetic recording / reproducing head, a MEMS (Micro Electro-Mechanical Systems) device, an ultrasonic probe, or the like.

Sectional drawing which shows the suitable aspect of the piezoelectric element of this invention The graph which shows the evaluation result of Examples 1-9

Explanation of symbols

1 Piezoelectric element 3, 5 Electrode 4 Piezoelectric material

Claims (12)

For ternary lead zirconate titanate (X) represented by the general formula Pb (Ni, Nb) O ₃ —PbZrO ₃ —PbTiO ₃ ,
(A) component: Pb in excess of the stoichiometric ratio;
(B) component: Zn,
(C) Component: At least one rare earth element selected from the group consisting of Ce, Yb, and Dy is added ,
For 100 parts by mass of the ternary lead zirconate titanate (X),
The addition amount of the component (A) is more than 0 parts by mass and less than 8.0 parts by mass in terms of oxide amount.
The addition amount of the component (B) is more than 0 parts by mass and less than 4.0 parts by mass in terms of oxide amount.
The addition amount of the component (C) is more than 0 parts by mass and 2.0 parts by mass or less in terms of oxide amount (the addition amount in terms of oxide amount is the amount of oxide when the above component is added in the form of oxide) The lead zirconate titanate composition characterized by the above. The amount of the component (A) is not more than 3.0 parts by mass 1.0 part by mass or more in amount of oxide basis,
The amount of component (B) is not more than 1.5 parts by 0.5 parts by mass or more in amount of oxide basis,
2. The lead zirconate titanate composition according to claim 1, wherein an addition amount of the component (C) is 0.25 parts by mass or more and 0.75 parts by mass or less in terms of oxide amount. A baked product produced by compressing a raw material powder containing the constituent elements of ternary lead zirconate titanate (X) and the components (A) to (C) into a predetermined shape, and firing the resulting compression molded body The lead zirconate titanate-based composition according to claim 1 or 2 , wherein the composition is a knot. 4. The lead zirconate titanate composition according to claim 3 , wherein the raw material powder contains components (A) to (C) in the form of oxides and / or acid salts. 5. The lead zirconate titanate composition according to claim 3 or 4 , wherein a firing temperature of the compression-molded body is 700 to 900 ° C. The lead zirconate titanate composition according to any one of claims 3 to 5 , wherein the firing atmosphere of the compression molded body is an oxygen-containing atmosphere. A method for producing a lead zirconate titanate composition according to claim 1 or 2 ,
A molding step of compression-molding a raw material powder containing the constituent elements of ternary lead zircon titanate (X) and the components (A) to (C) into a predetermined shape;
A method for producing a lead zirconate titanate-based composition comprising: a firing step of firing the compression-molded body obtained in the molding step.   The method for producing a lead zirconate titanate-based composition according to claim 7, wherein in the firing step, the compression-molded body is fired at a firing temperature of 700 to 900 ° C.   The method for producing a lead zirconate titanate-based composition according to claim 7 or 8, wherein, in the firing step, the compression-molded body is fired in an oxygen-containing atmosphere. For ternary lead zirconate titanate (X) represented by the general formula Pb (Ni, Nb) O ₃ —PbZrO ₃ —PbTiO ₃ ,
(A) component: Pb in excess of the stoichiometric ratio;
(B) component: Zn,
(C) Component: At least one rare earth element selected from the group consisting of Ce, Yb, and Dy is added ,
For 100 parts by mass of the ternary lead zirconate titanate (X),
The addition amount of the component (A) is more than 0 parts by mass and less than 8.0 parts by mass in terms of oxide amount.
The addition amount of the component (B) is more than 0 parts by mass and less than 4.0 parts by mass in terms of oxide amount.
The addition amount of the component (C) is more than 0 parts by mass and 2.0 parts by mass or less in terms of oxide amount (the addition amount in terms of oxide amount is the amount of oxide when the above component is added in the form of oxide) in is obtained by conversion.) the piezoelectric body characterized by. 11. The piezoelectric body according to claim 10, wherein a firing temperature during production is 800 to 900 ° C., and a piezoelectric constant d ₃₃ is 600 pm / V or more. A piezoelectric element comprising the piezoelectric body according to claim 10 and an electrode that applies an electric field to the piezoelectric body.

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